Jffanttfactttre of dyesttjffs



Patented May 20, 1930 UNITED STATESIIPATENT OFFICE PAUL iuwrasxy AND Aaron KRA'USE, or

L'tfnwIesHArnN-oN-TnE-nniun, enn- MANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC., 01 NEW YORK, N. Y., A.

CORPORATION OF DELAWARE :MANUFACTURE OF DYESTUFFS 1T0 Drawing. Application filed J'ime 11, 1928, Serial 1T0. 284,656, and in Germany June 27, 1927.

We have foundthat new and well-defined colored compounds are obtained by allowing aliphatic amines, in particular primary amines such as monomethylor monoethyl-am- 5 inc to act on naphthazarine under mild conditions as regards the temperature used which should not exceed 100 C. so that the reaction does practically not leadto the formation of vat dyestuffs. By the action of 1 monomethylamine on naphthazarine in this manner, a di-monomethyl-amino-hydroxynaphthoquinone or a tri'-monomet-hylaminonaphthoquinone are obtained. Condensing catalysts having a reducing action such as for 1:; example zinc dust or stannous chlorid, or substances regulating the-amount of aliphatic amine entering into the naphthazarine molecule such as boric acid are preferably added to the reaction mixture, though the reaction proceeds also without the said addition. The

' new compounds possess excellent tinctorial properties, and they may also be employed with advantage as intermediate products in the dyestufi industry. The products are s eciallysuitable for the production of-valua le 'dyeings and prints on cellulose esters or ethers, strong tinctorial effects in varying shades and of excellent fastness being obtained with the usual methods of dyeing cellulose esters or'ethera. I v v The following examples will further illustrate the nature of this invention which however is not restricted thereto; The parts are by weight. V

7 Example I I 10 parts of naphthazarine, 7 5 parts of a- 30 per cent aqueous solution of monomethylam- 40 inc and 1 part of zinc dust, are heated and stirred at 60 centigrade in a closed vessel for 20 hours. The deposited reaction prod:

not is filterexl by suction, and washed with cold water; it can be freed from sparin lysoluble lay-products by extraction with iling mono'chlorbenzene. The crude product obtained on concentrating the monochlorben- I zene liquor, furnishes, on crystallization from glacial acetic acid, oron sublimation in a high vacuum, the pure dyestufl in the form of dark a'cic'ular crystals of metallic lustre, with av melting point of 224 to 226 centitrade. It is insoluble in aqueous caustic soda. With concentrated sulfuric acid it fur 10 parts of naphthazarine, 75 parts of a 30 per cent aqueous solution of monomethylamine and 1 part of crystallized boric acid are heated and stirred at from 50 to 60 centi-v grade for 10 to 20 hours in a closed vessel. After cooling .andfiltering by suction, the crude productis separated from s soluble .by-products by boilingwit monochlorbenzene. The dye'stiiif which separates outon cooling is purified by recrystal lization from monoclorbenzene or b sublimation ina high vacuum, and is. t us obr arin'gly tained in the formof dark red-needles melty ing at 248 to 252 centigradm Aecordin to I analysis, it is :a di-monomethylaminm droxy-naphthoquinone. The reaction prob ably proceeds according to the following equation:

I n v 'The dyestuff gives a blue-violet solution inwarm dilute-icaustic soda solution, and a red solution in sulfuric acid. The solution in monochlorbenze'ne is red with a bluish tinge. This substance can be converted, more or less completely, into the bluish-green dyestufi de- 7. As a new article of manufacture trimonomethyl-amino-naphthoquinone forming I dark acicular needles of metallic lustre sub,-

limable in a high vacuum, of a melting point between 224 and 226 (3., soluble in co'ncen-.

trate'd sulfuric acid to an orange, solution filllgling blue on the addition of formaldey e. I

' In testimony whereof we have hereunto set our hands. I

. PAUL NAWIASKY.

ABTUR KRAUSE.

scribed in Example 1, by energetictreatment I with a dilute alcoholic solution [of methylamine with the addition of zinc dust, at

from to centigrade. The separation may be effected, for example,by utilizing the different solubility ofithe two products in monochlorbenzene. which the red "dye- I stufi' is considerably less soluble.

i 1. A process of .What we claim is compounds which consists in acting on naphproducing new colored thazarine' at temperatures not exceeding G. with primary aliphatic amines.

2. A process of producing new colored I compounds which consists in acting on naphthazarine at temperatures not exceeding 100- C. with primary aliphatic'amines in the press ence of condensing catalysts.

' 4 3. A process of producing new colored compounds which consists in acting on naphtha zarine at temperatures not exceeding 100 I C. with monomethylamine in aqueous solution in the presence of condensing catalysts. I v 4. A process of producing. new colored compounds which'consists in acting on naphthazarine at temperaturesnot exceeding 100 C. with monomethylamine in aqueq B9111:

tion in the presence of zinc dust.

. phatic, amines at 100C. I I

I v I I 6'. As 'a new article of m a.nufacture coliored compounds forming-(dark needles sub-'- a 5. As a new article of manufacture 00.19- ored compounds forming dark needles sub-' limable in a high vacuum and obtainable by acting on naphthazarine with primary alitemperatures not exceeding limable in a'high vacuum having 'amelting point between 224 and 226 :0. and obtain-- able b acting on naphthazarine with monomethy amine at temperatures not exceeding 

